The research first conducted the sulfur-fixing experiment of bio-mass coal briquette in a tubular furnace. The impacts of three additives Al2O3, Fe2O3 and MnO2 on the sulfur retention by calcium-based sorbent in briquette were investigated, and only Al2O3 displayed the enhancement of sulfur retention. The TGA experiment was further carried out, and proved that the high-temperature decomposition of CaSO4 in the deoxidization atmosphere was effectively inhibited with the addition of Al2O3. The XPS and XRD analyses of briquette ash showed that due to the interaction among Al2O3, CaSO4 and CaO, the composite CaSO4.3CaO.3Al2O3 which has more thermal stability was formed. With its wrapping or binding onto the surface of CaSO4 crystal, the decomposition of CaSO4 was mitigated.